A generalizable strategy toward highly tough and heat-resistant stereocomplex-type polylactide/elastomer blends with substantially enhanced melt processability

Abstract

Sustainable stereocomplex-type polylactide (SC-PLA) has been recognized as a potential substitute for some traditional engineering plastics, however its widespread application still faces several hurdles primarily related to poor melt processability (i.e., the unfavorable melt memory effect in SC crystallization as well as the low melt strength) and insufficient fracture toughness. To overcome these hurdles, an equimolar poly(l-lactide)/poly(d-lactide) (PLLA/PDLA) blend toughened with poly(ethylene-co-vinyl acetate) (EVA) has been chosen as a model system and a facile strategy has been devised by incorporating trace amounts (i.e., 0.5 wt%) of epoxy-functionalized oligo(styrene-acrylic) (ESA) into the PLLA/PDLA/elastomer blends through direct melt-blending at 200 °C. Such a one-pot blending not only facilitates the stereocomplexation between PLLA and PDLA chains but also permits the highly efficient reaction between terminal hydroxyl groups of some enantiomeric PLAs and epoxy groups of ESA before their stereocomplexation. This results in the in situ generation of large amounts of long-chain-branched PLA-graft-ESA copolymer in the SC-PLA matrix. Very impressively, the generation of this PLA-graft-ESA copolymer gives rise to a substantial improvement in the melt memory effect of the SC-PLA matrix. This copolymer behaves as a compatibilizer to stabilize regular PLLA/PDLA chain clusters in blend melts and hence to stimulate the exclusive formation of SC crystallites in melt-processed blend products. In addition, long PLA branches endow the matrix with a considerably enhanced melt viscosity owing to the increased interchain entanglement density. Consequently, highly stereocomplexed SC-PLA/EVA products with exceptional impact toughness and heat resistance as well as robust mechanical strength have been prepared by injection molding. More notably, this strategy can be generalized to various SC-PLA-based blends, irrespective of whether the elastomers have reactive groups. Overall, these exciting findings illustrate a promising avenue toward the design and applications of high-performance SC-PLA-based materials with excellent melt-processability via the generation of unique graft copolymers having long PLLA and PDLA branches.